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Fundamentals of

Analytical
Chemistry

Eighth Edition

Chapter14 p

CHAPTER

Principles of Neutralization
Titrations
Chapter14 p

9Acids and bases are very important in the environment. Acid


rain falling on the surface waters of lakes and ribers can cause
these waters to become acidic.
9Lime stone (calcium carbonate), which reacts with CO2 and H2O
to form bicarbonate. Bicarbonate in turn neurtalizes acids to
maintain the pH relatively constant.
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Figure 9F-1
Changes in p H of lakes
between 1930 and 1975.
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Figure 9F-2
Effect of pH of lades on their fish population.
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Figure 9F-3
Effect of presence of limestone on pH of lakes in the
United States. Shaded areas contain little limestone.
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Figure 9F-4
Sulfur dioxide emissions from selected plants in the United States Have
dropped below the levels required by law.

Titrimetric Method
Titrimetric methodsofanalysisarecapable
ofrapidandconvenientanalyte
determinationswithhighaccuracyand
precision.
Titrimetric analysisisbasedonthe
completereactionbetweentheanalyte and
areagent,thetitrant.

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aA +tT products
whereAandTrepresenttheanalyte
andtitrant,respectively,andaandtare
thestoichiometric coefficients.
Titrationsareoftenclassifiedbythe
natureofthistitrationreaction:acid
base,redox,precipitation and
complexation reactions arethemost
commonreactiontypes.
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Volumetric Titration
Forvolumetrictitrations,theamount,nA,
ofanalyte inthesamplecanbecalculated
using
nA =a/tCTVT

whereCT istheconcentrationofthetitrant,andVT is
thevolumeoftitrant neededtoreachtheendpoint.
Againaandtarethestoichiometric coefficients.
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Quantitativedeterminationoftheanalyte
concentrationrequiresthefollowing:
Thereisastoichiometric reactionbetweenanalyte and
titrant.Thisreactionshouldbefastandcomplete,and
thevaluesofaandtmustbeknown.
Theconcentrationofthetitrant solution,CT,mustbe
knownaccurately.Thetitrant solutionmustbe
standardized eitherbypreparingitusingaprimary
standardor,morecommonly,titratingitagainsta
solutionpreparedwithaprimarystandard.
Theendpoint volumemustbemeasuredaccurately
usinganappropriatechemicalindicatoror
instrumentalmethod.Ifaninstrumentalmethodis
usedtofollowtheprogressofthetitrationreaction,a
titrationcurvemaybegenerated,whichallowsforthe
analysisofmixturesand/orthedetectionof
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interferences.

Typical setup for carrying out a titration.


The apparatus consists of a buret, a buret
stand and clamp with a white porcelain base
to provide an appropriate background for
viewing indicator changes, and a widemouth Erlenmeyer flask containing a
precisely known volume of the solution to
be titrated. The solution is normally
delivered into the flask using a pipet, as
shown in FIGURE 2-22.

Figure 13-1
The titration process.

Chapter14 p 339

Detail of the buret graduations.


Normally, the bret is filled with titratnt
solution to within 1 or 2 mL of the
zero position at the top. The initial
volume of the buret is read to the
nearest 0.01 mL. The reference point
on the meniscus and the proper
position of the eye for reading are
depicted in figure 2-21.

Figure 13-1
The titration process.

Chapter14 p 339

Before the titration begins. The


solution to be titrated, an acid in
this example, is placed in the flask
and the indicator is added as
shown in the photo. The indicator
in this case is phenolphthalein,
which turns pink in basic solution.

Figure 13-1
The titration process.

Chapter14 p 339

During titration. The titrant is added to


the flask with swirling until the color
of the indicator persists. In the initial
region of the titration, titrant may be
added rather rapidly, but as the end
point is approached, increasingly
smaller portions are added; at the end
point, less than half a drop of titrant
should cause the indicator to change
color.

Figure 13-1
The titration process.

Chapter14 p 339

Figure 13-1
The titration process.

Titration end point. The end point is achieved when the barely
perceptible pink color of phenolphthalein persists. The flask on
the left shows the titration less than half a drop prior to the end
point; the middle flask shows the end point. The final reading of
the buret is made at this point, and the volume of base delivered
in the titration is calculated from the difference between the
initial and final buret readings. The flask on the right shows what
happens when a slight excess of base is added to the titration
mixture. The solution turns a deep pink color, and the end point
has been exceeded. In color plate 9, the color change at the end
339
point is much easier to see than in this black-and-white version.

Figure 13-2
Two types of titration curves.

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Equivalence point -

End point

Equivalence point End point


Figure 13-3
Titration curve for the
titration of 50.00 mL
of 0.1000 M AgNO3
with 0.1000 M
KSCN.
Chapter14 p 352

ExampleApplication:Analysisof
ChlorideinSurfaceWaters
Chloride isfrequentlyamajoranioninsurfaceand
groundwater;certainlyisamajorconstituentof
seawater.
Althoughchlorideinfreshwaterisusuallyof
geologicalorigin,runofffromroadssaltedduringthe
wintermaysignificantlyincreasethechloridecontent
ofsurroundingstreams,riversandlakes.
Ahighchlorideconcentrationmayimpartanoticeably
saltytastetopotablewater,andcanalsodamage
metallicpipesandgrowingplants.
Chapter14 p

ExampleApplication:Analysisof
ChlorideinSurfaceWaters(contd)
Argentometric titration ofwatersamplesisastandard
methodforchloridedetermination;
Concentrationsinthelowppm rangemaybedetected
usingpotentiometric titration.

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Chapter14 p 354

Equivalence point -

End point

Equivalence point End point


Figure 13-4
Titration curve for A,
50.00mL of 0.0500 M NaCl
with 0.1000 M AgNO3, and B,
50.00mL of 0.00500 M NaCl
with 0.0100 M AgNO3.
Chapter14 p 355

Figure 13-5
Effect of reaction
completeness on
precipitation titration
curves. For each curve,
50.00m of a 0.0500 M
solution of the anon was
titrated with 0.1000 M
AgNO3. Note that smaller
values of Ksp give much
sharper breaks at the end
point.
Chapter14 p 356

EndpointDetection
Avarietyofchemicalindicatorsareusedto
indicatetheendpointofargentometric titrations,
includingtheFajans,Volhard,andMohr methods
Asilverwireorringisasufficientindicator
electrodeforpotentiometric titrationsusing
AgNO3,whileafluorideISEissuitablefor
potentiometric endpointdetectionforfluoride
analysisusingLa3+orPb2+ titrant solutions.

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adsorption

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without

()

()
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Thiocyanate.Iron(III) Complex
a. Thiocyanate reacts with iron(III) to produce a deep, red color:
Fe3+ + SCN1-

FeSCN2+ (red)

The red color can be used to detect the presence of iron (III)
In titrations

Chapter14 p

Testing for iron(III) ions with thiocyanate ions


This provides an extremely sensitive test for iron(III) ions in
solution. If you add thiocyanate ions, SCN-, (from, say,
sodium or potassium or ammonium thiocyanate solution) to
a solution containing iron(III) ions, you get an intense blood
red solution containing the ion [Fe(SCN)(H2O)5]2+.

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adsorption

adsorbed

Indicator fluorescein

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adsorbed

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adsorbed

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adsorption
adsorbed

adsorbed
adsorbed
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adsorption

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2-Furoic acid

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Thestandardreagentsusedinacid/base
titrationsarealwaysstrongacidsor
strongbase,mostlycommonlyHCl,
HClO4,H2SO4,NaOH,andKOH.
Weakacidsandbasesareneverusedas
standardreagentsbecausetheyreact
incompletelywithanalytes
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Acid/Base Indicators
HIn + H2O ' In- + H3O+
acid color

base color

In + H2O ' InH+ + OHbase color

acid color

Ka = [H3O+][In-]/[HIn]
[H3O+] = Ka ([HIn]/ [In-])
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Figure 14-2
Indicator color as a function of pH
(pKa=5.0).
Acompletecolorchange
whenthepHofthesolution
inwhichitisdossolved changes
from4to6.

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Figure 14-1
Color change and
molecular model for
phenolphthalein.

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Colorless Pink
Magenta

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Red Yellow
Red

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Yellow Blue

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2.28

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pH 7.00

pH 2.28

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Beyond the equivalence point, we first calculate


pOH and then pH.
pH =pKw pOH = 14.00 pOH
Kw=[H3O+][OH-]
- log Kw = -log [H3O+][OH-] = -log[H3O+]-[OH-]
pKw = pH + pOH
-log 10-14 = pH + pOH =14
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Chapter14 p 374

Figure 14-3
Titration curves for
HCl with NaOH.
Curve A:50.00mL of
0.0500 M HCl with
0.1000 M NaOH.
Curve B: 50.00 mL of
0.000500 M HCl with
0.001000 M NaOH.

Chapter14 p 376

Figure 14-4
Titration curves for
NaOH with HCl.
Curve A:50.00 mL
of 0.0500 M NaOH
with 0.1000 M
HCl. Curve B:
50.00 mL of
0.00500 M NaOH
with 0.0100 M
HCl.

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HA+H2O H3O+ + A-

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A-+H2O HA + OH-

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Henderson-Hasselbalch equation
is used to calculate the pH of
buffer solutions.

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HA+H2O H3O+ + A-

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A-+H2O HA + OH-

-5
10-14/6.31x10
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Kb

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Figure 14-5
Curve for the titration
of acetic acid with
sodium hydroxide.
Curve A: 0.1000 M
acid with 0.1000 M
base. Curve B:
0.001000 M acid with
0.001000 M base.

Chapter14 p 381

Figure 14-6
The effect of acid strength (dissociation constant) on
titration curves. Each curve represents the titration of
50.00 mL of 0.1000 M acid with 0.1000 M base. Chapter14 p 382

Figure 14-7
The effect of base strength (Kb) on titration curves.
Each curve represents the titration of 50.00mL of
0.1000 M base with 0.1000 M HCl.
Chapter14 p 385